Anionic hydrophilic monomer (ASPU), cationic (CSPU) and nonionic (NSPU) polyurethane/nano SiO2 composite emulsions were synthesized by 2,2-dihydroxy methyl propionic acid (DMPA)， methyl diethanolamine (MDEA) and polyethylene glycol (YMER N-120) with sol-gel procedures, respectively. KH-550 was the capping agent of prepolymer. SEM， TGA， FTIR， DSC， XRD and tensile testing machine were performed on the films to test the surface appearance, thermal properties, the structure and mechanical properties of the composite films. The results showed that the average particle size of NSPU was the biggest. The order of crystallinity: NSPU>CSPU>ASPU; The order of tensile strength and shore hardness: ASPU>CSPU>NSPU. Anionic hydrophilic monomer and cationic (CSPU) polyurethane/nano SiO2 composite films had better thermal properties, water resistance and mechanical properties；nonionic (NSPU) polyurethane/nano SiO2 composite films had better flexibility, alkali resistance and acid resistance.